We have made a detailed study of the extended X-ray absorption fine spectra (EXAFS) at the K edge of aqueous Y ion and at L3 edges of aqueous lanthanide ions and thereby elucidated the systematic changes in their hydration structures. Anomalous peaks arising from double-electron excitation (2p, 4d → 5d, 5d) appear in the EXAFS signals of La3+-Tb3+ between 5–7 Å−1. We established a removal process of double-electron excitation from EXAFS spectra. Using that process, we confirmed that the intensity and energy position of the extracted double-electron excitation are comparable to previously reported data. The presence of double-electron excitation engenders a smaller error than the errors estimated in the fitting process. Consequently, double-electron excitation does not seriously affect the determination of the structures of REE3+ aquo ions in the first coordination sphere. Subsequent EXAFS analyses of hydrated REE3+ ions suggest that the hydration numbers, the interatomic distances, and the Debye-Waller factors decrease from 9.7, 2.55 Å, and 9.0 × 10−3 Å2 for La3+ to 7.9, 2.31 Å, and 5.7 × 10−3 Å2 for Lu3+. These parameters change as a sigmoid curve with increasing atomic number. The hydration structures of REE3+ ions are inferred to change from the nonahydrated structure for La3+-Nd3+ to the octahydrated structure for Tb3+-Lu3+ through intermediate structures for Sm3+, Eu3+, and Gd3+. In addition, the hydration state of Y3+ closely resembles that of Ho3+ because the two have almost identical ionic radii.